Aerosol hairspray for styling and/or shaping hair

ABSTRACT

An aerosol hairspray product for styling and/or shaping hair wherein the product comprises: a container; a spraying device; a propellant; a hairstyling formulation comprising: (a) at least about 50% water; and (b) from about 0.01% to about 20% of a hairstyling polymer, wherein the hairstyling polymer is selected from the group consisting of: acrylates copolymers of two or more monomers of (meth)acrylic acid or one of their simple esters; acrylates/hydroxyesters acrylates copolymers of butyl acrylate, methyl methacrylate, methacrylic acid, ethyl acrylate and hydroxyethyl methacrylate; polyurethane-14/AMP-acrylates polymer blend; and mixtures thereof. The product comprises about 2% or less alcohol, or is substantially free of alcohol, and the product comprises 54% or less VOC.

FIELD OF THE INVENTION

An aerosol hairspray product for styling and/or shaping hair.

BACKGROUND OF THE INVENTION

Hairstyling products such as hairsprays are used for achieving differenthairstyles and for holding hair strands in place for a period of time.Typically, hairsprays comprise film-forming polymers, which when appliedto keratin-containing fibres, such as human hair, form fibre-fibrewelds. These welds ‘glue’ the fibres together and hence impart hold tothe hairstyle.

Aerosol hairspray products usually comprise a pressure-resistantcontainer, a nozzle, a propellant, and a hairstyling formulation. Ahairspray composition is normally ejected from such products viaaerosol-forming nozzle. See, for example, US2009/0104138A1. Commonlyused propellants include the volatile organic compounds (VOCs) propane,butane, 1,1-difluoroethane, and dimethylether. However, VOCs are knownto react with certain nitrogenic oxides, which in turn may result in theformation of ground-level ozone—a potential source of health problems.Alcohols are also often used in the hairstyling formulation, for exampleto reduce surface tension. However, a high proportion of alcohol mayleave the hair feeling dry and brittle and some alcohols may cause anallergic response in some users. Also, ethanol is flammable and is aVOC.

There is a constant need, therefore, for more environmentally friendly,more sustainable, and affordable hairspray products, in particular foraerosol hairspray products comprising low levels of VOC and alcohol.However, altering one or more features of an aerosol hairspray productcan be challenging since the interrelationship therebetween affects theproduct performance. For example, utilising a different propellant mayresult in an unacceptable droplet size of the ejected composition andconsequently unsatisfactory hold. Furthermore, certain hairstylingpolymers may be incompatible with hairspray products comprising lowlevels of VOC and/or alcohol.

When considering the aforementioned needs, therefore, good hairsprayperformance should be maintained. Performance benefits may include, forexample: excellent hold; long-lasting hold; good humidity resistance;shapeable hold; acceptable drying time; excellent soft, natural hairfeel; acceptable and/or non-stickiness/tackiness of the hands and hair.Of particular relevance to consumers is natural hair feel andnon-tackiness of the hands and hair.

SUMMARY OF THE INVENTION

In a first aspect, the invention relates to an aerosol hairspray productfor styling and/or shaping hair wherein the product comprises:

-   -   i. a container comprising a container wall which encloses a        reservoir for storing a hairstyling formulation and a        propellant;    -   ii. the hairstyling formulation comprising:        -   (a) at least about 50% water by total weight of the            hairstyling formulation and propellant; and        -   (b) from about 0.01% to about 20% of a hairstyling polymer            by total weight of the hairstyling formulation and            propellant, wherein the hairstyling polymer is selected from            the group consisting of: acrylates copolymers of two or more            monomers of (meth)acrylic acid or one of their simple            esters; acrylates/hydroxyesters acrylates copolymers of            butyl acrylate, methyl methacrylate, methacrylic acid, ethyl            acrylate and hydroxyethyl methacrylate;            polyurethane-14/AMP-acrylates polymer blend; and mixtures            thereof; and    -   iii. a propellant, which is selected from the group consisting        of compressed gas propellants, liquefied gas propellants, and        mixtures thereof; and    -   iv. a spraying device attached to the container for dispensing        the hairstyling formulation from the reservoir of the container;        and wherein the product comprises about 2% or less alcohol by        total weight of the hairstyling formulation and propellant, or        is substantially free of alcohol;        wherein the product comprises 54% or less volatile organic        compound by total weight of the hairstyling formulation and        propellant.

In a second aspect, the invention relates to a method for styling haircomprising:

-   -   i. applying to hair an ejected composition, wherein the ejected        composition is ejected by the hairspray product according to the        first aspect;    -   ii. drying the ejected composition on the hair.

In a third aspect, the invention relates to the use of the productaccording to the first aspect for fixing and/or shaping a hairstyle.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments of the present invention will now be described, by way ofexample only, with reference to the drawings in which:

FIG. 1 shows a cross-sectional side-view of an embodiment of a spraynozzle;

FIG. 2 shows a cross-sectional view along line A-A in FIG. 1;

FIG. 3 shows a cross-sectional view along line B-B in FIG. 2;

FIG. 4 shows the enlarged section A of FIG. 1;

FIG. 5 shows the enlarged section A of FIG. 1 with a modification;

FIG. 6 shows a schematic view of an embodiment of the spray nozzle;

FIG. 7 shows a schematic view of an embodiment of the spray nozzle.

DETAILED DESCRIPTION OF THE INVENTION

All percentages are by weight of the total composition/formulation,unless stated otherwise. All ratios are weight ratios, unless statedotherwise. All ranges are inclusive and combinable. The number ofsignificant digits conveys neither a limitation on the indicated amountsnor on the accuracy of the measurements. The term “molecular weight” or“M. Wt.” as used herein refers to the weight average molecular weightunless otherwise stated. “QS” or “QSP” means sufficient quantity for100%. +/− indicates the standard deviation.

All numerical amounts are understood to be modified by the word “about”unless otherwise specifically indicated. Unless otherwise indicated, allmeasurements are understood to be made at 25° C. and at ambientconditions, where “ambient conditions” means conditions under about oneatmosphere of pressure and at about 50% relative humidity. All suchweights as they pertain to listed ingredients are based on the activelevel and do not include carriers or by-products that may be included incommercially available materials, unless otherwise specified.

Embodiments and aspects described herein may comprise or be combinablewith elements or components of other embodiments and/or aspects despitenot being expressly exemplified in combination, unless otherwise statedor an incompatibility is stated.

The term “aerosol” as used herein, means a suspension of fine dropletsin a gas. The aerosol hairspray product atomises the hairsprayformulation i.e. creates an aerosol. Due to surface tension, dropletsare normally substantially spherical. As used herein, the “droplet size”is defined as the median diameter of ejected droplets.

The term “aerosol hairspray product” does not encompass mousse or foamproducts. The term “mousse” or “foam” as defined herein means adispersion of gas bubbles in a liquid. Commonly, mousse or foamcompositions usually comprise greater than 0.3% surfactant by weight.The surfactant results in the formation of spherical bubbles which formthe mousse or foam consistency. However, foams and mousses can also beformed from surfactant-free formulations via other means, for examplespecial actuators, using proteins e.g. egg white protein. Typically,hairstyling products that eject a mousse/foam also comprise from about6% to about 16% by weight propellant.

The term “aerosol hairspray product” does not encompass gel products orproducts comprising or ejecting a gel composition. Gels may be dispensedvia a pump spray actuator. Hand gel formulations typically have aviscosity of from about 8,000 mPa·s to about 20,000 mPa·s depending onthe desired performance. The ejected composition of spray gels typicallyhas a droplet size of at least about 80 micron in diameter.

As used herein, the term “on-hair drying time” means the amount of timeit takes for the ejected composition to dry on the hair. The on-hairdrying time is measured by spraying a specific pattern on the hair andthen timing when the hair ceases to feel tacky and damp in the hand.

As used herein, the term “ejection flow” is defined as the loss in totalweight of the aerosol hairspray product after 5 seconds of spraying.This value is normally divided by 5 to give grams per sec. The ejectionflow should achieve a balance between excellent hold and sufficientlyfast drying time. For example, if too much ejected composition isapplied to the hair in a short period, then the on-hair drying time maybe unacceptably long.

Herein, “comprising” means that other steps and other ingredients whichdo not affect the end result can be added. This term encompasses theterms “consisting of” and “consisting essentially of”. The compositions,methods, uses, and processes herein can comprise, consist of, andconsist essentially of the elements and limitations of the inventiondescribed herein, as well as any of the additional or optionalingredients, components, steps, or limitations described herein.

The term “polymer” as used herein shall include all materials made bythe polymerisation of monomers as well as natural polymers. Polymersmade from only one type of monomer are called homopolymers. A polymercomprises at least two monomers. Polymers made from two or moredifferent types of monomers are called copolymers. The distribution ofthe different monomers can be calculated statistically orblock-wise—both possibilities are suitable for the present invention.Except if stated otherwise, the term “polymer” used herein includes anytype of polymer including homopolymers and copolymers.

The term “hairstyling polymer” as used herein means hair-fixing polymerswhich form films on a surface. In the context of hair, this surface isthe surface of individual hair fibres or a plurality thereof. Thepolymer causes them to be glued together to build welds, which arecross-links that provide the hold benefit. In concert, these welds forma ‘hairnet’ to provide hair hold and volume benefits to the user. Whenthe net of welds is effectively formed, the hold and volume benefits canlast all day and offer good resistance to environmental humidity.

The hairspray product according to the present invention is suitable forapplication onto human hair. The term “suitable for application to humanhair” as used herein means that the compositions or components thereofso described are suitable for use in contact with human hair and thescalp without undue toxicity, incompatibility, instability, allergicresponse, and the like.

The term “maximum incremental reactivity” value or “MIR” value asdefined herein, means a measure of the increase in ozone formation perunit weight of a hydrocarbon when added to the atmosphere. Hence, MIRmeasured the ozone forming potential of a compound. A similarmeasurement to MIR is “photochemical ozone creation potential” or“POCP”.

The term “global warming potential” or “GWP” as defined herein is ameasure of how much a given mass of a compound is calculated tocontribute to global warming compared to that of the same mass of carbondioxide. The global warming potential of carbon dioxide, therefore,is 1. As used herein, the GWP values are those calculated for a 100 yeartime horizon, unless otherwise stated.

As used herein, the term “volatile organic compound” or “VOC”, as usedherein means any organic compound having a initial boiling point lessthan or equal to 250° C. measured at a standard pressure of 101.3 kPa.In an embodiment, “VOC” means any compound having a vapour pressure of0.01 kPa or more at 293.15 K (i.e. 20° C.). “Organic” as used hereinmeans any compound containing at least the element carbon and one ormore of hydrogen, halogen, oxygen, sulfur, phosphorus, silicon, ornitrogen. Certain volatile compounds of organic chemistry falling withinthis definition are known to photochemically react with nitrogenicoxides in the presence of sunlight and, in turn, this producesground-level ozone and photochemical smog. In fact, in the UnitedStates, the definition of VOC for US legislative purposes (U.S. EPA 40CFR 51. 100[s]) defines only those organic compounds without negligiblephotochemical reactivity. Examples of compounds considered to be VOCsfor the purposes of this application include: ethanol, dimethylether,1,1-difluoroethane, 1,1,1,2-tetrafluoroethane, pentane, n-butane,iso-butane, propane, trans-1,3,3,3-tetrafluoropropene, free formic acid(i.e. not its salt). Certain fragrances and plant extracts are alsoVOCs.

The term “non-flammable”, as used herein in terms of the aerosolhairspray product, means the product contains 1% or less flammablecomponents and the chemical heat of combustion is less than 20 kJ/g andis also considered non-flammable following an ignition distance testand, if necessary, the enclosed space test. If the chemical heat ofcombustion is less than 20 kJ/g, then the aerosol is classified asflammable if ignition occurs at a distance of 15 cm or more. Theignition distance test for spray aerosols is a standard test wherein theaerosol is sprayed in the direction of an ignition source at intervalsof 15 cm to observe if ignition and sustained combustion takes place.Ignition and sustained combustion is defined as when a stable flame ismaintained for at least 5 seconds. The ignition source is defined as agas burner with a blue, non-luminous flame 4-5 cm in height. If noignition occurs in the ignition distance test, the enclosed space testshall be performed and in this case, the aerosol is classified asflammable if the time equivalent is less than or equal to 300 s/m³ orthe deflagration density is less than or equal to 300 g/m³; otherwisethe aerosol is classified as non-flammable. The enclosed space ignitiontest is a standard test wherein the contents of an aerosol dispenser aresprayed into a cylindrical test vessel containing a burning candle. Ifan observable ignition occurs, the elapsed time and amount discharged isnoted. These definitions are that of the UN Manual of Tests andCriteria, Part III, Section 31. The chemical heat of combustion can bedetermined via the standard method ASTM D 240.

The term “substantially free from”, “substantially free of”, orgrammatical equivalents thereof, as defined herein means less than about1%, or less than about 0.8%, or less than about 0.5%, or less than about0.3%, or about 0%.

The inventors have surprisingly overcome the above hindrances andanswered the aforementioned needs by carefully selecting the specificcombination of mutually compatible features such that the interactiontherebetween results in a hairspray with good performance. Firstly, thehairspray formulation pursuant to the present invention is water-basedi.e. it is an aqueous system rather than a predominantly alcohol-basedsystem as is conventionally employed. This water-based system providessafety, sustainability, environmental and cost advantages. Secondly, thehairspray product comprises about 2% or less alcohol by total weight ofthe hairstyling formulation and propellant, or is substantially free ofalcohol. This additionally provides highly consumer-relevant benefitssince alcohol has the reputation of causing the hair to become brittleand dry, particularly for naturally fine and/or dry hair. Without beingbound by theory it is believed that low alcohol concentrations help toreduce drying out effect i.e. reduce a perceived brittle, harsh feel ofthe hair. Consumers prefer a more natural hair feel and look. Theinventors have found that selected hairstyling polymers are particularlysuited for use in such hairspray formulation. The inventors have foundthat hairstyling polymer M. Wt., glass transition temperature,water-compatibility and chemistry are important factors in order tocreate a low viscosity, fully dissolved, readily sprayable hairstylingformulation that provides an ejected composition that, following normalapplication onto hair, results in good hairstyle hold, good humidityresistance, no residues or flaking on hair, and yet is easily washedout. The selected hairstyling polymers meet these criteria—inparticular, the hairstyling polymers, despite being highly compatible inthe water-based hairstyling formulation, also provide humidityresistance in high relative humidity for the hairstyle and yet areeasily washed out with normal shampoo. Moreover, the hold offered by theselected hairstyling polymers is good, but without causing a ‘helmethead’-type feeling for the consumer. Performance benefits achieved bythe hairspray product pursuant to the present invention includeexcellent hair feel, particularly natural hair feel, and excellentnon-stickiness of the hands and hair, good hold and shapeable hold.Furthermore, it has been surprisingly found that the selected polymerscan be blended together in order to provide more natural hair feel orgreater hairstyle hold. The hairstyling polymers can be blended intospecific mixtures, for example ‘soft’ hairstyling polymers may beblended with ‘hard’ hairstyling polymers.

A particular benefit of the hairstyling polymers as described herein isthe low tackiness on hands and/or hair achieved. Surprisingly thetackiness on hands and/or hair of the present invention is lower thanachieved by conventional ethanol-based aerosol hairsprays. This issurprising because the hold provided by the present invention iscomparable to conventional aerosol hairsprays.

Each of the features of the aerosol hairspray product, as well as otherrelevant components, are described in detail hereinafter.

According to the first aspect, the present invention relates to anaerosol hairspray product, wherein the product comprises less than 54%VOC by total weight of the hairstyling formulation and propellant. In anembodiment, the aerosol hairspray product has a maximum incrementalreactivity (MIR) value of less than 1, or less than 0.8, or less than0.7, or less than 0.4. The MIR value of an aerosol hairspray product canbe calculated by multiplying the fraction by weight of each component ofthe hairspray product by its MIR value. MIR values of common componentsof hairspray products include: 2-aminomethyl propanol: about 15.08;water: 0.00; acetone: 0.43; ethanol: 1.69; isopropanol: 0.71. More MIRvalues are listed below. For example, a product comprising 0.2% of2-aminomethyl propanol and no other components with an MIR value abovezero, would have an MIR value of 0.03. In an embodiment, the hairstylingformulation and propellant have a heat of combustion of from about 5kJ/kg to about 20 kJ/kg and/or the product is non-flammable.

The surface tension and viscosity of the hairstyling formulation can beimportant because following spraying, the ejected composition formsdroplets, which land on the hair. The ejected composition should thenspread out along each individual hair fibre in order to form a thinlayer of coating on the hair, which dries quickly and also forms weldswith other similarly coated hair fibres. In an embodiment, the surfacetension, measured according to standard test ISO 304 at 20° C., of thehairstyling formulation is from about 20 mN/m to about 50 mN/m, or fromabout 20 mN/m to about 40 mN/m, or from about 28 mN/m to about 40 mN/m,or from about 30 mN/m to about 40 mN/m. ISO 304 is a standard testmethod for measuring surface tension of pure liquids or solutions.

In an embodiment, the kinematic viscosity, measured according tostandard test DIN EN ISO 3104, of the hairstyling formulation is fromabout 1 mm²/s to about 25 mm²/s, or from about 1 mm²/s to about 15mm²/s, or from about 2 mm²/s to about 10 mm²/s, or from about 1 mm²/s toabout 4 mm²/s, or from about 1.2 mm²/s to about 3 mm²/s. DIN EN ISO 3104is a standard test method for measuring kinematic viscosity of liquids.The kinematic viscosity can be important because when the hairstylingformulation is too viscous then the hairstyling formulation is too thickand cannot be sprayed and/or is clogging—inhomogeneous ejectedformulation results e.g. irregular spray beam, “spitting” rather thanspraying, and/or ejection of lumps. This can be especially importantwhen a compressed gas propellant is utilised because the propellant isin gaseous form and hence cannot function as a co-solvent.

The median droplet size of the ejected composition is from about 10micron to about 80 micron, or from about 15 micron to about 60 micron,or from about 15 micron to about 50 micron, or from about 20 micron toabout 35 micron. Droplets smaller than about 10 micron are not suitablefor the present invention due to safety concerns—the droplets may enterthe lungs and cause health problems. Droplets larger than about 100micron are too large and consequently unsuitable. In an embodiment, thedroplet size is not greater than 80 micron. Hairspray products which arepump sprays normally have a droplet size which is too large and arehence unsuitable. The aerosol hairspray product is not a pump spray.

Droplet size is measured using a technique based on laser diffraction.Scattered light is focused by a focusing lens in a Fourier arrangementand picked up by the detector array. The angle at which aparticle/droplet diffracts light is inversely proportional to its size.The detector array is made up of over 30 individual detectors, each ofwhich collects the light scattered by a particular range of angles. Thescattering pattern from the spray is captured, which is what ismeasured. Measuring the angle of diffraction determines the size of theparticle/droplet. A Malvern Spraytec EPCS 4.0 is used with a 450 mm lenstype, serial number 237. Software: RT Sizer 5.0. Test duration: 4000 ms.Data acquisition rate: 200 Hz. Minimum droplet size able to be measured:0.8 micron. Maximum droplet size able to be measured: 300 micron.Distance between nozzle and laser beam: 140 mm.

The ejection flow of the hairspray product is from about 0.10 g/sec toabout 0.40 g/sec, or from about 0.20 g/sec to about 0.35 g/sec, or fromabout 0.20 g/sec to about 0.30 g/sec, or from about 0.20 g/sec to about0.25 g/sec. If the ejection flow is greater than about 0.45 g/sec, thenthe on-hair drying time will be too long for consumer satisfaction.Ejection flow can typically be adjusted by altering the pressure insidethe container (increased pressure correlates with faster ejection flow)and/or the diameter opening in the spraying device and/or orifices inthe actuator (lower diameter correlates with slower ejection flow).

The on-hair drying time of the ejected composition may be from about 0.5min to about 7 min, or from about 1 min to about 5 min, or from about 1min to about 2 min.

The hairstyling formulation comprises from about 0.01% to about 20%, orfrom about 1% to about 16%, or from about 2% to about 12%, or from about3% to about 8%, or from about 4% to about 7% of a hairstyling polymer,by total weight of the hairstyling formulation and propellant.

The hairstyling polymer is selected from the group consisting of:acrylates copolymers of two or more monomers of (meth)acrylic acid orone of their simple esters; acrylates/hydroxyesters acrylates copolymersof butyl acrylate, methyl methacrylate, methacrylic acid, ethyl acrylateand hydroxyethyl methacrylate; polyurethane-14/AMP-acrylates copolymerblend; and mixtures thereof. Balance® CR from Akzo Nobel is an acrylatescopolymer of two or more monomers of (meth)acrylic acid or one of theirsimple esters. In an embodiment, polyurethane-14/AMP-acrylates copolymerblend is blend of an acrylates copolymer and a polyurethane polymer.Acudyne™ 1000 is an acrylates/hydroxyesters acrylates copolymer of butylacrylate, methyl methacrylate, methacrylic acid, ethyl acrylate andhydroxyethyl methacrylate. DynamX® H2O from Akzo Nobel is blend of anacrylates copolymer and a polyurethane polymer i.e.polyurethane-14/AMP-acrylates copolymer blend. Balance® CR from AkzoNobel is an acrylates copolymer of two or more monomers of (meth)acrylicacid or one of their simple esters. In an embodiment, hairstylingformulation comprises two of more different hairstyling polymers,wherein the hairstyling polymer is selected from the group consistingof: acrylates copolymers of two or more monomers of (meth)acrylic acidor one of their simple esters; acrylates/hydroxyesters acrylatescopolymers of butyl acrylate, methyl methacrylate, methacrylic acid,ethyl acrylate and hydroxyethyl methacrylate;polyurethane-14/AMP-acrylates polymer blend; and mixtures thereof. In anembodiment, hairstyling formulation comprises all three of hairstylingpolymers listed above. In an embodiment, the product is substantiallyfree of octylacrylamide/acrylate/butylaminoethyl methacrylatecopolymers. Amphomer® is an octylacrylamide/acrylate/butylaminoethylmethacrylate copolymer.

In an embodiment, the hairstyling formulation comprises from about 3% toabout 20% of a sole hairstyling polymer, wherein the sole hairstylingpolymer is selected from the group consisting of: acrylates copolymersof two or more monomers of (meth)acrylic acid or one of their simpleesters; and acrylates/hydroxyesters acrylates copolymers of butylacrylate, methyl methacrylate, methacrylic acid, ethyl acrylate andhydroxyethyl methacrylate. In an embodiment, the hairstyling formulationcomprises from about 4% to about 7% of a hairstyling polymer being thesole hairstyling polymer and the hairstyling polymer being an acrylatescopolymer of two or more monomers of (meth)acrylic acid or one of theirsimple esters. As used herein “sole hairstyling polymer” means that thehairstyling formulation comprises only one type of hairstyling polymerand other hairstyling polymers are not present, and wherein the otherhairstyling polymers do not fall within the definition provided for thesole hairstyling polymer.

In an embodiment, the hairstyling formulation comprises a mixture ofhairstyling polymers. The mixture may comprise a hard hairstylingpolymer and a soft hairstyling polymer. As used herein “hard hairstylingpolymer” is a hairstyling polymer which provides excellent hairstylehold and this hairstyle hold is more pronounced as the concentration ofthe hard hairstyling polymer in the hairstyling formulation increases.However, high concentrations of hard hairstyling polymer typically havenegative effect on the hair feel i.e. consumers find the palpable feelof the hair unacceptable e.g. rough. As used herein “soft hairstylingpolymer” is a hairstyling polymer which provides excellent i.e. naturalhair feel, particularly soft and/or smooth hair feel, but typically thehairstyle hold provided is limited.

In an embodiment, the hairstyling formulation comprises from about 3% toabout 20% of a sole hairstyling polymer, wherein the sole hairstylingpolymer is a hard hairstyling polymer.

The softness and hardness of the hairstyling polymer depends on the M.Wt. and the glass transition temperature of the hairstyling polymer, andalso the chemistry of the hairstyling polymer i.e. the chemistry of themonomers.

In an embodiment, the hard hairstyling polymer has a glass transitiontemperature of greater than or equal to 10° C. and the soft hairstylingpolymer has a glass transition temperature of less than 10° C. “Glasstransition temperature” or “T_(g)”, as used herein, means the lowesttemperature at which a polymer can be considered flowable, which meansthe polymer chains can slide past each other when a force is applied.The T_(g) as used herein may be measured according to DIN EN 61 006.

In an embodiment, the M. Wt. of the hairstyling polymer(s) is from about10 thousand g/mol to about 200 thousand g/mol, or from about 20 thousandg/mol to about 150 thousand g/mol. In an embodiment, the hardhairstyling polymer has M. Wt. of from about 90 thousand g/mol to about200 thousand g/mol. In an embodiment, the soft hairstyling polymer hasM. Wt. of from about 10 thousand g/mol to about 90 thousand g/mol.

The hairstyle hold provided by increasing amounts of the softhairstyling polymer in the hairstyling formulation increases, but thenplateaus. In other words, the soft hairstyling polymer has a maximumhairstyle hold that it can provide. Consequently, it can be advantageousto provide a mixture of a hard hairstyling polymer and a softhairstyling polymer.

In an embodiment, the hard hairstyling polymer is selected from thegroup consisting of: acrylates copolymers of two or more monomers of(meth)acrylic acid or one of their simple esters;acrylates/hydroxyesters acrylates copolymers of butyl acrylate, methylmethacrylate, methacrylic acid, ethyl acrylate and hydroxyethylmethacrylate; and mixtures thereof. In an embodiment, the softhairstyling polymer is selected from the group consisting of: apolyurethane-14/AMP-acrylates polymer blend; latex hairstyling polymers;polyesters; and mixtures thereof. In an embodiment, the soft hairstylingpolymer is a polyurethane-14/AMP-acrylates polymer blend or a latexhairstyling polymer. In an embodiment, the soft hairstyling polymer is apolyurethane polymer. The polyurethane polymer may be apolyurethane-14/AMP-acrylates polymer blend. In an embodiment, thehairstyling formulation comprises an additional soft hairstylingpolymer, wherein the additional soft hairstyling polymer is selectedfrom the group consisting of: PVP (polyvinylpyrrolidone) polymers;PVP-VA-copolymers (vinylpyrrolidone/vinylacetate copolymers);polyesters; and mixtures thereof.

In an embodiment, the hairstyling formulation comprises a mixture of: asoft hairstyling polymer being a polyurethane-14/AMP-acrylates polymerblend or a latex hairstyling polymer; and a hard hairstyling polymerselected from the group consisting of: acrylates copolymers of two ormore monomers of (meth)acrylic acid or one of their simple esters; andacrylates/hydroxyesters acrylates copolymers of butyl acrylate, methylmethacrylate, methacrylic acid, ethyl acrylate and hydroxyethylmethacrylate. In an embodiment, the mixture is the combination of: asoft hairstyling polymer being a polyurethane-14/AMP-acrylates polymerblend or a latex hairstyling polymer; and both of the following two hardhairstyling polymers: acrylates copolymers of two or more monomers of(meth)acrylic acid or one of their simple esters; andacrylates/hydroxyesters acrylates copolymers of butyl acrylate, methylmethacrylate, methacrylic acid, ethyl acrylate and hydroxyethylmethacrylate. In an embodiment, the mixture comprises a polyester and anacrylates copolymers of two or more monomers of (meth)acrylic acid orone of their simple esters. In an embodiment, the polyester is apolyester-5 polymer. In an embodiment, the mixture comprises at least 2,or at least 3, different hairstyling polymers. An example of apolyester-5 polymer is AQ® 48 Ultra Polymer from Eastman ChemicalCompany.

In an embodiment, the weight ratio of hard hairstyling polymer to softhairstyling polymer (hard:soft) in the mixture is from about 10:1 toabout 1:10, or from about 10:1 to about 1:2. In an embodiment where themixture comprises at least 2 different hairstyling polymers, or only 2different hairstyling polymers, the weight ratio of hard:soft may befrom about 10:0.5 to about 9:3, or about 10:1 to about 9:2. In anembodiment where the mixture comprises at least 3 different hairstylingpolymers, or only 3 different hairstyling polymers, the weight ratio ofhard:soft may be from about 10:1 to about 6:4, or about 10:2 to about8:3.

In an embodiment, the hairstyling formulation further comprises anadditional ingredient selected from the group consisting of:octylacrylamide/acrylate/butylaminoethyl methacrylate copolymers,panthenol compounds, silicone compounds, latex compounds, and mixturesthereof. In an embodiment, the hairstyling formulation further comprisesa panthenol compound. In an embodiment, the panthenol compound isselected from the group consisting of: panthenol, a pantothenic acidderivative, and mixtures thereof. In an embodiment, the panthenolcompound is selected from the group consisting of: D-panthenol([R]-2,4-dihydroxy-N-[3-hydroxypropyl)]-3,3-dimethylbutamide),D/L-panthenol, pantothenic acids and their salts, panthenyl triacetate,royal jelly, panthetine, pantotheine, panthenyl ethyl ether, pangamicacid, pantoyl lactose, Vitamin B complex, and mixtures thereof. In anembodiment, the hairstyling formulation comprises a mixture comprising ahard hairstyling polymer, panthenol, and optionally a soft hairstylingpolymer. In an embodiment, the hairstyling formulation comprisespanthenol. The panthenol compound is able to have a ‘softening’ effecton the hard hairstyling polymer. The hairstyling formulation maycomprise from about 0.1% to about 0.6%, or from about 0.1% to about0.3%, of a panthenol compound by total weight of the hairstylingformulation and the propellant. The weight ratio of hard hairstylingpolymer to panthenol compound may be from about 100:6 to about 100:1, orfrom about 100:4 to about 100:20. In an embodiment, the panthenolcompound is either D-panthenol or D/L-panthenol. In an embodiment, thehairstyling formulation further comprises a silicone compound. Thesilicone is useful because it gives a smoother feel and also shine tothe hair. In an embodiment, the silicone compound is a dimethiconecompound. In an embodiment, the silicone compound is a PEG dimethicone,for example PEG-12 dimethicone. In an embodiment, the hairstylingformulation further comprises a octylacrylamide/acrylate/butylaminoethylmethacrylate copolymer. Amphomer® is anoctylacrylamide/acrylate/butylaminoethyl methacrylate copolymer.

In an embodiment, the hairstyling polymer is a water-compatiblehairstyling polymer, alternatively a water-soluble hairstyling polymer.In an embodiment, the hairstyling formulation is substantially free froma water-incompatible hairstyling polymer. Balance® CR, Acudyne™ 1000,DynamX® H2O from Akzo Nobel are water-compatible.

In an embodiment, the hairstyling formulation further comprises a latexhairstyling polymer. In an embodiment, the latex hairstyling polymer isa polyurethane polymer and/or an aqueous polyurethane dispersion. In anembodiment, the polyurethane polymer is Polyurethane-48. Baycusan® C1008 is a Polyurethane-48, which is an aqueous polyurethane dispersion.

In an embodiment, the product comprises less than about 0.5% of acationic surfactant by total weight of the hairstyling formulation andpropellant. In an embodiment, the hairstyling formulation comprises apolyurethane polymer and the hairstyling formulation is substantiallyfree of a cationic surfactant. In an embodiment, the sole hairstylingpolymer is neither a latex hairstyling polymer nor a polyurethanepolymer. In an embodiment, the hairstyling formulation is substantiallyfree of a polyurethane polymer. This is because, in certaincircumstances, polyurethane polymers can cause residues on the hairafter the ejected formulation has dried on the hair. Such residues areunsightly and not preferred by consumers since they can be confused withdandruff.

The tackiness on hands and/or hair of the present invention is lowerthan achieved by conventional ethanol-based aerosol hairsprays. In anembodiment, the product comprises from about 20% to about 50% VOC, bytotal weight of the hairstyling formulation and the propellant and theliquefied gas propellant is DME. The low tackiness on hands and/or hairbenefit is also achieved for this embodiment.

Amphoteric polymers as well as anionic polymers such as Balance® CR arenormally present in their neutralized or partially neutralized form. Inan embodiment, the hairstyling polymer is at least 60%, or at least 80%neutralized.

Suitable neutralisers include potassium hydroxide, sodium hydroxide,triisopropanolamine (TIPA), 2-aminobutanol, 2-aminomethyl propanol(AMP), aminoethylpropandiol, dimethyl stearamine (Armeen 18 D), sodiumsilicate, tetrahydroxypropyl ethylenediamine (Neutrol® TE), ammonia(NH₃), triethanolamine, trimethylamine (Tris Amino Ultra),aminomethylpropandiol (AMPD). In an embodiment, the neutralising agentis 2-aminobutanol, ammonia, or 2-aminomethyl propanol.

The hairstyling formulation may further comprise a surfactant. Thehairstyling formulation may comprise 1% or less surfactant, or 0.6% orless, or 0.4% or less, or 0.3% or less, by total weight of thehairstyling formulation and propellant. In an embodiment, the surfactantis selected from the group consisting of cationic surfactants, non-ionicsurfactants, anionic surfactants, and mixtures thereof. Cationicsurfactants may be selected from the group consisting of cetrimoniumchloride (e.g. Quartamin 60L-G from Kao; DEHYQUART A-CA/DETEX; ARQUAD16-25 LO); cocamidopropyl hydroxysultaine (e.g. REWOTERIC AM CAS);cocamidopropyl betaine (e.g. TEGO BETAIN F 50); betaine; and mixturesthereof. Non-ionic surfactants may be selected from the group consistingof: castor oil PEG-40 H (e.g. NEODOL 91-8); laureth-4 (e.g. DEHYDOL LS 4DEO N); laureth-9; decyl glucoside (e.g. Plantacare 2000); polysorbate20 (e.g. TWEEN 20 PHARMA from UNIQEMA); PEG-25 hydrogenated castor oil(e.g. SIMULSOL 1292 DF from SEPPIC); PEG-40 hydrogenated castor oil(e.g. CREMOPHOR CO 410 from BASF); PPG-1-PEG-9-laurylglycolether (e.g.Eumulgin L); siloxane polyalkyleneoxide copolymer (Silwet® L7604 fromMomentive); and polydimethylsiloxane methylethoxylate (Silwet® L7600from Momentive); and mixtures thereof. A suitable anionic surfactant isdioctyl sodium sulfosuccinate (DOSS or1,4-dioctoxy-1,4-dioxobutane-2-sulfonic acid), an example of which isAerosol OT-70 PG from Cytec. In an embodiment, the surfactant isselected from the group consisting of: castor oil PEG-40 H; cetrimoniumchloride; laureth-4; laureth-9; decyl glucoside; cocamidopropylhydroxysultaine; polysorbate 20; siloxane polyalkyleneoxide copolymer;dioctyl sodium sulfosuccinate; and mixtures thereof. In an embodiment,the surfactant is selected from the group consisting of: castor oilPEG-40 H; decyl glucoside; cocamidopropyl hydroxysultaine; polysorbate20; siloxane polyalkyleneoxide copolymer; dioctyl sodium sulfosuccinate;and mixtures thereof. In an embodiment, the surfactant is selected fromthe group consisting of: siloxane polyalkyleneoxide copolymer; anddioctyl sodium sulfosuccinate; and mixtures thereof.

The hairstyling formulation comprises at least about 50%, or from about50% to about 99%, or from about 60% to about 99%, or from about 70% toabout 99% water by total weight of the hairstyling formulation andpropellant. When the product is substantially free of VOC, thehairstyling formulation may comprise from about 90% to about 99% water,by total weight of the hairstyling formulation and propellant.

The product comprises about 2% or less alcohol by total weight of thehairstyling formulation and propellant. In an embodiment, the productcomprises about 1.8% or less, or about 1.5% or less, or about 1% orless, alcohol by total weight of the hairstyling formulation andpropellant, or is substantially free of alcohol. In an embodiment, thehairstyling formulation is substantially free of ethanol and propanol.In an embodiment, the product comprises about 5% or less, or 2% or less,or about 1.8% or less, or about 1.5% or less, or about 1% or less,aliphatic alcohol by total weight of the hairstyling formulation andpropellant. “Aliphatic alcohol” as used herein means an alcoholcomprising no aromatic group.

The hairstyling formulation may comprise at least one preservative. Thepreservative may be present in an amount of less than about 1.5%, or 0%to 1%, or 0.01% to 1% by total weight of the hairstyling formulation andpropellant. Suitable preservatives include: phenoxyethanol (e.g. Euxyl®PE 9010), benzyl alcohol, propyleneglycol, PHMB (Poly-aminopropylbiguanide), Optiphen (Phenoxyethanol+caprylyl glycol) from ISP, Symtriol(1,2 octanediol and 1,2 hexanediol,Methylbenzyl alcohol) from Symrise,octylsalicylate,1,3-bis(hydroxymethyl)-5,5-dimethylimidazolidine-2,4-dione (DMDMhydantoin; Nipaguard® DMDMH by Clariant), EDTA (Rexat), butylene glycol(Dekaben LMB), and parben types e.g. methylparaben (e.g. PHB-methylester from Schtitz & Co., or SLI Chemicals, or Nipagin® M),propylparaben (PHB-propylester from Solvadis Specialties).

The hairstyling formulation may further comprise at least one perfume orfragrance. The aerosol hairspray product may comprise a maximum of about0.5% perfume or fragrance, or from about 0% to about 0.4%, or from about0.03% to about 0.3%, by total weight of the hairstyling formulation andpropellant.

The hairstyling formulation may further comprise vitamins and aminoacids such as: water soluble vitamins such as vitamin B1, B2, B6, B12,C, pantothenic acid, pantothenyl ethyl ether, panthenol, biotin, andtheir derivatives, water soluble amino acids such as asparagine,alanine, indole, glutamic acid and their salts, water insoluble vitaminssuch as vitamin A, D, E, and their salts and/or derivatives, waterinsoluble amino acids such as tyrosine, tryptamine, viscosity modifiers,dyes, non-volatile solvents or diluents (water soluble and insoluble),pearlescent aids, foam boosters, additional surfactants or non-ioniccosurfactants, pediculocides, pH adjusting agents, perfumes,preservatives, chelants, proteins, skin active agents, sunscreens, UVabsorbers, vitamins, niacinamide, caffeine and minoxidil. The productmay comprise from about 0.01% to about 5% vitamins and/or amino acids,by total weight of the hairstyling formulation and propellant.

The aerosol hairspray product may further comprise pigment materialssuch as inorganic pigments, nitroso-, monoazo-, disazo-compounds,carotenoid, triphenyl methane, triaryl methane, chemicals of thequinoline, oxazine, azine, or anthraquinone type, as well as compoundswhich are indigoid, thionindigoid, quinacridone, phthalocianine,botanical, natural colors, and water-soluble components. The product maycomprise from about 0.0001% to about 5% pigment materials, by totalweight of the hairstyling formulation and propellant. The formulation(s)described herein may also contain antimicrobial agents which are usefulas cosmetic biocides. The product may comprise from about 0.01% to about5% antimicrobial agents, by total weight of the hairstyling formulationand propellant.

The hairstyling formulation may have a pH of from about 6 to about 10,or from about 7 to about 10, or from about 7 to about 9.

The product comprises a propellant, which is selected from the groupconsisting of compressed gas propellants, liquefied gas propellants, andmixtures thereof.

The product may comprise a compressed gas propellant. The compressed gaspropellants may be selected from the group consisting of air, nitrogen(N₂), nitrous oxide (N₂O), carbon dioxide (CO₂), and mixtures thereof.In an embodiment, the compressed gas propellant is air or nitrogen (N₂).In an embodiment, the compressed gas propellant is nitrogen (N₂). In anembodiment, the compressed gas propellant is not carbon dioxide(CO₂)—particularly when a hairstyling polymer may precipitate due toeffect of the CO₂ in lowering the pH of the hairstyling formulation.Also CO₂ typically permeates through plastic material to a greater orlesser extent i.e. 0% permeation is typically unachievable. The term“air” is defined herein as a gas comprising approximately 78% nitrogen,21% oxygen, and 1% of carbon dioxide, argon and other trace elements.Since the content of air can vary, in an embodiment the compressed gaspropellant is nitrogen gas. As defined herein, the compressed gases N₂,CO₂, and N₂O are all non-flammable. N₂O has a GWP of 298. When thepropellant is air, a maximum of 1 g is utilised as propellant.

CFCs are not suitable propellants for the present invention due to theirozone depleting properties. For example, CFC-12 has a GWP of 10,900. Inan embodiment, the product has a GWP of 100 or less, or 50 or less, or20 or less, or 10 or less, or 5 or less.

The product may comprise a liquified gas propellant. The liquefied gaspropellant may be selected from the group consisting of dimethylether(DME), 1,1-difluoroethane (HFC-152a), 1,1,1,2-tetrafluoroethane(HFC-134a), pentane, n-butane, iso-butane, propane,trans-1,3,3,3-tetrafluoropropene (HFO-1234ze), and mixtures thereof. Inan embodiment, the liquefied gas propellant is dimethylether (DME) or1,1-difluoroethane (HFC-152a). In an embodiment, the liquefied gaspropellant is DME.

For the purposes of the present invention, all the liquified gaspropellants mentioned above are VOCs. Furthermore, as defined herein,n-butane is flammable (MIR=1.15, GWP=4); iso-butane is flammable(MIR=1.23); propane is flammable (GWP=3.3, MIR=0.49); HFC-134a isnon-flammable (GWP=about 1400, MIR=0.00); HFC-152a is flammable(GWP=about 120, MIR=0.02); HFO-1234ze is non-flammable (GWP=6,MIR=0.09); DME is flammable (GWP=1, MIR=0.81).

The product comprises 54% or less VOC by total weight of the hairstylingformulation and propellant. In an embodiment, the product comprises fromabout 20% to about 50%, or from about 25% to about 45%, or from about35% to about 42%, VOC, by total weight of the hairstyling formulationand propellant. In another embodiment, the propellant is a liquefied gaspropellant and the liquefied gas propellant is DME, and wherein productcomprises from about 25% to about 45%, or from about 35% to about 42%,DME. In another embodiment, the product comprises less than 15% VOC, oris substantially free of VOC, by total weight of the hairstylingformulation and propellant. In another embodiment, the product comprisesfrom about 1% to less than 15% of a VOC, by total weight of thehairstyling formulation and propellant. In an embodiment where thepropellant is a compressed gas propellant, the product comprises lessthan 15% of a VOC, by total weight of the hairstyling formulation andpropellant.

The present invention comprises a container comprising a container wallwhich encloses a reservoir for storing a hairstyling formulation and apropellant. In an embodiment, the container wall comprises predominantlyplastic material. In an embodiment, the container wall comprises atleast about 80% plastic material, or from about 85% to about 100%, bytotal weight of the container. The term “plastic” is defined herein asany polymeric material that is capable of being shaped or molded, withor without the application of heat, and then hardened into a desiredform including, polymers, resins, and cellulose derivatives. Usuallyplastics are homo- or co-polymers of high M. Wt. Cosmetic productscontained in plastic containers are known. Plastic is a particularlyadvantageous material for containing cosmetic products because a greatervariety of specific container forms may be created. The utilisation ofplastic material(s) for a hairspray container provides an excellentmeans to deliver ease-of-use benefits to the consumer. For example, itis very easy to provide tactile advantages e.g. grip features, contours,and these tactile advantages can be designed with a high degree ofspecificity and accuracy. Furthermore, a plastic container can easily bemoulded in one piece. Sealed plastic containers have a lower explosionpotential than metal containers because, upon application of excessivetemperature for example, due to the more elastic nature of plasticcompared to metal, the plastic material may expand at a weak point inthe container, e.g. where the container wall is thinner. Gradually andeventually the expansion at this weak point allows the high-pressuredcontainers to escape via the formation of a hole. Furthermore, aestheticbenefits can also be realised more easily when a plastic container isused, for example, a transparent and/or translucent container materialcould be employed, and in addition to many other aesthetic benefits.From an environmental perspective, utilisation of a container comprisingpredominantly plastic material has sustainability benefits and resultsin a reduced carbon footprint than alternative container materials.Plastic is also more easily recycled than metal.

In an embodiment, the plastic material is selected from the groupconsisting of polyolefins, polyesters, polyamide, polyvinylchloride,acrylic, polycarbonates, polyethylene naphthalate (PEN), polyethyleneterephthalate (PET), polystyrene, polyurethane, and mixtures thereof. Inan embodiment, the plastic material is selected from the groupconsisting of polyethylene terephthalate (PET), polyethylenenapththalate (PEN), and mixtures thereof. Polyethylene napththalate isavailable from Hoechst Trevira GmbH & Co. KG, under the trademarkPolyclear®, including Polyclear® N10, Polyclear® N90 and Polyclear®N100.

The container may comprise polymers made from components derived fromrenewable sources i.e. non-petroleum sources. As used herein the term“sustainable polymer” means polymers made from components e.g. monomers,derived from renewable sources. Examples of renewable, non-petroleumsources include plants and microorganisms. The renewable, non-petroleumplants sources may include sugar cane, beets, corn, potatoes, citrusfruit, and woody plants. For example, ethanol can be produced fromsugarcane. The ethanol may then be converted into ethylene, which can bepolymerized to form polyethylene (PE). The monomers from whichpolypropylene (PP), polyester, and polyethylene terephthalate (PET) aresynthesized, may also be derived from renewable sources. Sustainablepolymers may be synthesized from monomers derived from starch and/orcellulose, or by modification of the polymer itself. Cellulosics arethermoplastic resins manufactured by the chemical modification ofcellulose.

These sustainable plastic materials may be used as 100% of the plasticmaterial utilized for the container wall, or blended into thepetroleum-derived plastic material at varying levels in order to varyperformance and/or for economic reasons. Certain materials derived fromplant sources may be biodegradable. Sustainable polymers exhibitingbiodegradability include aliphatic polyesters such as polylactic acid(PLA), polyglycolic acid (PGA), polybutylene succinate (PBS) andcopolymers thereof, aliphatic-aromatic polyesters such as Ecoflex® fromBASF and Biomax® from DuPont, polyhydroxyalkanoate (PHA) and copolymersthereof. Thermoplastic starch (TPS) materials are also biodegradable, asare cellulosics. The incorporation of biodegradable sustainable polymersmay be at 100% of the utilized plastic material or in blends with othermaterials, in order to control the speed or degree of biodegradation, orfor economic reasons. The speed and degree of biodegradation must becompatible with the purpose and features of the present invention.Ecoflex® from BASF, for example, is a biodegradable plastic materialthat biodegrades in soil or compost. It is stable on shelf for one year.It is particularly suitable for bags and films.

Recycled plastic material can also be re-ground. This post-consumerregrind resin may also be suitable for the present invention either whenblended with other resins or used as 100% of the plastic materialutilised. Re-ground polyethylene at certain densities (r-HDPE, r-LLDPE,r-LDPE), reground polypropylene (r-PP), and reground polyethyleneterephthalate (r-PET) may be suitable.

Filler materials may be blended into the plastic material. Theadvantages of the incorporation of filler materials into plasticmaterial include: adjustment of physical properties of the plastic, suchas mechanical strength, density and cooling time, and also economicreasons. In an embodiment, the filler is selected from the groupconsisting of: starches, fibres from renewable sources such as hemp,flax, coconut, wood, paper, bamboo, and also inorganic materials such ascalcium carbonate, mica, and talc. In addition, gas fillers such as highpressure gas, foaming agents or microspheres may be added to the plasticmaterial.

Plastic materials can be defined by their glass transition temperature(Tg) and/or M. Wt. When the container wall comprises at least about 80%plastic material, or from about 85% to about 100% plastic material, bytotal weight of the container, the wall thickness of the container wallmay also be important. In an embodiment, the plastic material is PET,wherein the glass transition temperature of from about 70° C. to about80° C., and wherein the wall thickness is from about 0.5 mm to about 3.2mm. An example PET container comprises the following wall thicknesses:shoulder about 0.65 mm; sidewall about 0.50 mm; outside base about 1.09mm; base pushup about 2.90 mm. The container may be moulded to create aspecific ergonomic external form or contour, for example, hand-shapedcontours. Said form facilitates effective and precise use of thehairspray product, for example by providing more grip or non-slip. Othertactile features may also be provided on the surface of the container,for example pimples. In an embodiment, the container is not cylindricalin shape. Furthermore the container may be provided with specificaesthetic features, such as colour combinations, and transparent ortranslucent portions. In an embodiment, at least 50% of the containerwall is translucent, or transparent. When externally viewable,bag-on-valve systems are less favoured by consumers for aestheticreasons.

In an embodiment, the container wall comprises predominantly metalmaterial. In an embodiment, metal material is selected from the groupconsisting of aluminium, tin plated steel, and combinations thereof. Inan embodiment, the container wall comprises at least about 80%, or fromabout 85% to about 100% metal material, by total weight of thecontainer. In an embodiment, the container wall comprises at least about80% metal material by total weight of the container, and wherein themetal material is selected from the group consisting of: aluminium, tinplated steel, and combinations thereof; and wherein the propellant is aliquefied gas propellant, and wherein the liquefied gas propellant isselected from the group consisting of DME, 1,1-difluoroethane,1,1,1,2-tetrafluoroethane, pentane, n-butane, iso-butane, propane,trans-1,3,3,3-tetrafluoropropene, and mixtures thereof; or DME,1,1-difluoroethane, and mixtures thereof. In an embodiment, thecontainer wall comprises an inner surface, wherein the inner surface iscoated with a corrosion inhibitor. In an embodiment, the corrosioninhibitor is a polyamide-imide laquer. A suitable corrosion inhibitor isHOBA 8460, supplied by HOBA Lacke und Farben GmbH.

In an embodiment, the propellant and hairstyling formulation may freelycommunicate with one another inside the reservoir. In an embodiment, thepropellant and hairstyling formulation are stored in a singlecompartment. In an embodiment, the aerosol hairspray product does notcomprise a bag-on-valve system, especially when a portion of thecontainer wall is translucent, or transparent. In an embodiment, thereservoir comprises a plurality of compartments for storing thehairstyling formulation and the propellant. In an embodiment, thepropellant and hairstyling formulation are not stored in separatecompartments. In an embodiment, the reservoir does not comprise aplurality of compartments for storing the hairstyling formulation andthe propellant.

The pressure inside the reservoir can be measured with a pressure gauge(GCAS #60001439). The pressure inside the reservoir may be from about 1bar to about 16 bar at 50° C. When the propellant is a compressed gas,the pressure inside the container may be from about 6 bar to about 12bar, or from about 8 bar to about 10 bar, or from about 9 bar, at 50° C.When the propellant is a liquefied gas, the pressure inside thecontainer may be from about 1 bar to about 7 bar, or from about 3 bar toabout 5 bar, at 50° C. In an embodiment, the reservoir comprises amaximum volume of 220 ml of hairstyling formulation and propellant.

The product comprises a spraying device attached to the container fordispensing the hairstyling formulation from the reservoir of thecontainer. In an embodiment, the spraying device comprises a spraynozzle. In an embodiment, the spraying device comprises a sealing valveand an actuator. The sealing valve and actuator may or may not be madefrom plastic material. Valve and actuators are, for example, availablefrom Seaquist Closures (Freyung, Germany), Aptar, Precision and Coster(Switzerland). U.S. Pat. No. 3,819,090 relates to a valve cup device forpressurized dispensing containers comprising a one-piece molded plasticbody. U.S. Pat. No. 5,199,615A relates to an aerosol dispenser. Asuitable spraying device when the propellant is a liquefied gaspropellant is as follows: valve: Precision; stem: 0.010 inch; restrictedtail piece: 0.050 inch; vapour phase housing: 0.020 inch; actuator:Kosmos 0.016 inch Wirbel; diptube: capillar 0.060 inch. Suitablespraying devices include NAZ DR 5113″ and NAZ DR 5118 both from Aptar.The spray properties can be altered by utilising a vapour housing holein the stem, which can help to make a wet spray drier by using more gasfrom the vapour phase. In an embodiment where the propellant is aliquefied gas propellant, the spraying device comprises a vapour housinghole.

In an embodiment, the spray nozzle is a spray nozzle 2 for dispensing afluid comprising a first element 20, preferably a nozzle cup 20, and asecond element 22, preferably a pin 22, said first and second element20, 22 forming an assembly 80 comprising a fluid chamber 40, preferablya ring chamber, for receiving the fluid, at least one feeding channel 42for feeding the fluid from the fluid chamber 40 radially inward into aswirl chamber 44 and an outlet channel 18 with an entrance end 54 facingthe swirl chamber 44 and an exit end 56 for discharging the fluid to theenvironment 58 of the spray nozzle 2, characterized in that the outletchannel 18 tapers in the flow direction of the fluid and the degree oftapering is either constant in the flow direction, or the degree oftapering decreases in the flow direction.

In an embodiment, the exit end 56 has a maximum diameter (d_(max))between about 0.1 mm and about 0.8 mm, preferably between about 0.1 mmand about 0.25 mm, more preferably between about 0.1 mm and about 0.2mm, still more preferably between about 0.12 mm and about 0.15 mm.

In an embodiment, the inner face 62 of the outlet channel 18 includes anangle (β), said angle (β) varying between about 70° and about 130°,preferably between about 80° and about 120°, more preferably betweenabout 80° and about 110°.

In an embodiment, the feeding channel 42 comprises a first section 48and a second section 50 following the first section 48 in the flowdirection and abutting the swirl chamber 44, the width (w1) of the firstsection 48 decreasing in the flow direction and the width (w2) of thesecond section 50 being constant or decreasing to a lesser extent in theflow direction.

In an embodiment, the length (1) of the second section 50 in the flowdirection is equal to or smaller than the width (w2) of the secondsection 50 or/and the height (h) of the first or/and second section 48;50 is decreasing in the flow direction or/and the width (w2) of thesecond section 50 is equal to the height (h) of the second section 50.

In an embodiment, the ratio of the diameter (d_(s)) of the swirl chamber44 to the diameter (d_(max)) of the exit end 56 is about 2.5 to about3.5.

In an embodiment, the ratio of the sum of the cross-sectional areas ofthe at least one feeding channel 42 at their exit end 46 to thecross-sectional area of the exit end 56 of the outlet channel 18 isbetween about 1.5 and about 2.7, preferably between about 1.7 and about2.6.

In an embodiment, the bottom 26 of the first element 20 exerts apretension against the flow direction of the fluid of about 0.5 N toabout 1.5 N, preferably of about 1 N.

In an embodiment, the bottom 26 of the first element 20 is conical inlongitudinal direction 6 forming with the second element 22 a contactarea which is defined by the penetration of the second element 22 duringthe assembly, which generate pretension between the first element 20 andthe second element 22 due slightly bending the bottom 26 of the firstelement 20 in longitudinal direction 4.

In an embodiment, one of the first and second element 20, 22 comprisesan elastic portion, the elastic portion being elastically deformed bythe other element 22, 20 when the elements 20, 22 are assembled, theprotrusions 28 or/and the section of the first element 20 carrying theprotrusions 28 preferably forming the elastic portion.

In an embodiment, the first element 20 and the second element 22 areconnected via a flexible connecting piece 38, preferably a strip, theconnecting piece 38 more preferably being integrally formed or moldedwith the first and second element 20, 22.

In an embodiment, an outlet layer 64 with a first hole 66, a channellayer 68 with a second hole 70 and slots 72 and an inlet layer 74 withholes 76 are provided, said layers 64, 68, 74 being sandwiched such thatthe first hole 66 forms the outlet channel 18, the second hole 70 formsthe swirl chamber 44, the slots 72 form the feeding channels 42 and theholes 76 in the inlet layer 74 form inlet holes for feeding the fluidfrom the fluid chamber 40 into the feeding channels 42, the layers 64,68, 74 preferably being separable from each other or/and each of thelayers 64, 68, 74 preferably being replaceable.

In an embodiment, there is provided an overlapping area 78 between theinlet holes and the feeding channels 42, the size of the overlappingarea 78 or/and the distance between the overlapping area 78 and theswirl chamber 44 preferably being adjustable, the inlet layer 74 and thechannel layer 68 more preferably being moveable, most preferablyrotatable, relative to each other in order to adjust the size of theoverlapping area 78 or/and the distance between the overlapping area 78and the swirl chamber 44.

In an embodiment, the spray nozzle 2 is made of a plastic materialselected from the following list: polyoxymethylene, polypropylene,polyethylene, polystyrene, acrylonitrile butadiene styrene, silicone,polyamide, polyethylene terephthalate, an elastomer or mixtures thereof.

Another embodiment of the first aspect relates to an aerosol hairsprayproduct for styling and/or shaping hair wherein the product comprises:

-   -   i. a container comprising a container wall which encloses a        reservoir for storing a hairstyling formulation and a        propellant;    -   ii. the hairstyling formulation comprising:        -   (a) at least about 50% water by total weight of the            hairstyling formulation and propellant; and        -   (b) from about 0.01% to about 20% of a hairstyling polymer            by total weight of the hairstyling formulation and            propellant, wherein the hairstyling polymer is selected from            the group consisting of: acrylates copolymers of two or more            monomers of (meth)acrylic acid or one of their simple            esters; acrylates/hydroxyesters acrylates copolymers of            butyl acrylate, methyl methacrylate, methacrylic acid, ethyl            acrylate and hydroxyethyl methacrylate; a            polyurethane/acrylates polymer blend; and mixtures thereof;            and    -   iii. a propellant, which is selected from the group consisting        of compressed gas propellants, liquefied gas propellants, and        mixtures thereof; and    -   iv. a spraying device attached to the container for dispensing        the hairstyling formulation from the reservoir of the container;        and wherein the product comprises about 2% or less alcohol by        total weight of the hairstyling formulation and propellant, or        is substantially free of alcohol;        wherein the product comprises 54% or less volatile organic        compound by total weight of the hairstyling formulation and        propellant. All the features of the first aspect described        herein are applicable to this embodiment also.

In the second aspect, the invention relates to a method for styling haircomprising the steps of: (i) applying to hair an ejected composition,which is ejected by the product according to the present invention; (ii)drying the ejected composition on the hair. The method may also comprisea step preceding step (i) wherein a hairdo or hairstyle is created. Themethod may also comprise a step preceding step (ii) but after step (i)wherein a hairdo or hairstyle is created.

In the third aspect, the invention relates to the use of the productaccording to the present invention, for fixing and/or shaping ahairstyle. In an embodiment of the third aspect, the use comprises usingthe product according to the present invention for fixing a hairstylefollowing the creation of a hairstyle. Alternatively, the use comprisesusing the product according to the present invention for creating andshaping a hairstyle.

A fourth aspect relates to a kit comprising at least one aerosolhairspray product, as described herein, and a communication describingthe use of the product. The kit may further comprise an item selectedfrom the group consisting of a shampoo, conditioner, mousse, gel, ahairstyling tool, blow dryer, curling tongs, and straightening irons.The hairstyling tool may be selected from the group consisting of hairbands, hair fasteners, combs, and brushes.

A fifth aspect relates to a hairstyling formulation comprising at least50% water and a mixture of hairstyling polymers, wherein the mixturecomprises a hard hairstyling polymer and a soft hairstyling polymer. Thehard hairstyling polymers and soft hairstyling polymers may be as perthe first aspect described herein. The hairstyling formulation accordingto the fifth aspect may be useful for hairspray products includingaerosols and pumps spray, and also mousses, gels, tonics and other formsof hairstyling formulation. In an embodiment of the fifth aspect, theinvention relates to the herein-described hairstyling formulation in thecontext of a hair styling product other than an aerosol hairspray. Forexample, mousses, gels and lotions comprising this hairstylingformulation are also useful styling products. In an embodiment, theinvention relates to a mousse, gel or lotion comprising a hairstylingformulation, wherein the hairstyling formulation comprises (a) at leastabout 50% water; and (b) from about 0.01% to about 20% of a hairstylingpolymer, wherein the hairstyling polymer is selected from the groupconsisting of: acrylates copolymers of two or more monomers of(meth)acrylic acid or one of their simple esters;acrylates/hydroxyesters acrylates copolymers of butyl acrylate, methylmethacrylate, methacrylic acid, ethyl acrylate and hydroxyethylmethacrylate; polyurethane-14/AMP-acrylates polymer blend; and mixturesthereof; and wherein the mousse, gel or lotion comprises about 2% orless alcohol, or is substantially free of alcohol and the mousse, gel orlotion comprises 7% or less VOC. Mousse products typical comprise apropellant, such as those propellants described in detail herein. Manyfeatures of the first aspect described herein are applicable to thisaspect also.

DETAILED DESCRIPTION OF THE DRAWINGS OF THE INVENTION

FIG. 1 to 4 show views of a first embodiment of the spray nozzle 2 fordispensing a fluid. In the figures, the opposing longitudinal directions4, 6, the opposing radial directions 8, 10 and the opposingcircumferential directions 12, 14 of the spray nozzle are indicated bycorresponding arrows. The longitudinal axis 16 of the spray nozzle 2extends in the longitudinal directions 4, 6, said longitudinal axis 16further forming the centre axis of the outlet channel 18.

The spray nozzle 2 is assembled from a first element 20 and a secondelement 22 thereby forming an assembly 80. The first element 20 is anozzle cup 20, i.e. having a cup-like structure with a first section 24extending in the circumferential directions 12, 14 and forming asurrounding wall and a second section 26 forming the bottom 26. Thesecond section 26 further comprises protrusions 28, said rib-likeprotrusions 28 extending in the longitudinal direction 6 and in theradial directions 8, 10. As can be best seen in FIG. 2, there areprovided grooves 30 in the circumferential directions 12, 14 between theprotrusions 28, said grooves being provided to form the feeding channels42 as will be described later. The protrusions 28 comprise an uppersurface serving as a support surface 32 for supporting the secondelement 22, said support surface 32 facing the second element 22.Further, the protrusions 28 comprise side surfaces 34 facing the grooves30 and feeding channels 42, respectively.

The second element 22 may be a pin 22 basically having a cylindricalform with a front face 36, said front face 36 bulging out in thelongitudinal direction 4. In this embodiment, the front face 36 has aform of a spherical cap. The second element 22 is inserted into thefirst element 20, so that the front face 36 is supported on the supportsurfaces 32 of the protrusions 28. In this connection it should bementioned, that the second element 22 may also be formed by a ball,which is pressed or clipped into the first element 20. Independent ofthe chosen form of the second element 22, it is preferred if the secondelement 22 could be snapped or clicked into its place within the firstelement 20, even if corresponding notches, snaps or the like forproviding a form-fit or/and a force-fit are not shown in the figures.

The first element 20 and the second element 22 may be connected via aflexible connecting piece 38, which—in this case—is formed by a strip.The connecting piece 38 is integrally formed or molded with the secondelement 22 and at least the first section 24 of the first element 20.Even the second section 26 of the first element 20 may be integrallyformed or molded with the first section 24 of the first element 20 andconsist of the same material. However, in this case the second section26 has been subsequently fastened to the first section 24 since thesecond section 26 is made of a different material, as will be describedhereinafter. Irrespective of the second section 26 being integrallyformed with the first section 24 or not, the first element 20 comprisesan elastic portion.

As already indicated above, the first element 20 is at least partiallymade of an elastic material being more elastic than the material of thesecond element 22. In this case, the second section 26 of the firstelement 20 with its protrusions 28 and its bottom section 26 carryingsaid protrusions 28 is made of the elastic material, said elasticmaterial being more elastic than the material of the second element 22and more elastic than the material of the first section 24 of the firstelement 20. Thus, the afore-mentioned elastic portion of the firstelement 20 is essentially formed of the protrusions 28 and its bottomsection carrying said protrusions 28. The elastic portion of the firstelement 20 is elastically deformed by the second element 22 when theelements 20, 22 are assembled.

Further, the bottom 26, i.e. second section 26, of the first element 20exerts a pretension against the flow direction of the fluid of about 0.5N to about 1.5 N, preferably of about 1 N. In other words, during theassembly of the spray nozzle 2, i.e. when the second element 22 isinserted into the first element 20 a bending of the bottom 26 of thefirst element 20 to a flat position occurs, thereby generating thatpretension against the second element 22. This pretension assuresadhesion of the first element 20 to the second element 22 when fluid isdispensed at high pressure.

Even if the pre-assembled state is not shown, it is preferred if thebottom section carrying said protrusions 28 is curved or convex towardsthe second element 22 and in the longitudinal direction 6 before thefirst and second element 20, 22 are assembled.

In one example, the spray nozzle 2 is assembled by inserting the pin 22into the nozzle cup 20 in the longitudinal direction 4 as shown in FIG.1, thereby creating a fluid chamber 40, feeding channels 42 and a swirlchamber 44, while the outlet channel 18 is already provided in thesecond section 26 of the nozzle cup 20. The fluid chamber 40 ispositioned in the radial directions 8, 10 between the first section 24of the nozzle cup 20 and the pin 22, so that the fluid chamber 40 isformed as a ring chamber. The fluid chamber 40 receives the fluid to bedispensed from a fluid storage chamber or container, which is not shownin the drawings. In the longitudinal direction 4 the fluid chamber 40abuts the radial outer ends of the feeding channels 42, so that there isa fluid connection between the fluid chamber 40 and the feeding channels42.

As can especially be seen in FIG. 2, the feeding channels 42 areextending radially inward to an exit end 46 of the feeding channels 42,where the feeding channels 42 abut the swirl chamber 44, so that thefluid may be fed from the fluid chamber 40 via the feeding channels 42into the swirl chamber 44. As shown in FIG. 3, the feeding channels 42are limited in the circumferential directions 12, 14 by the sidesurfaces 34 of the protrusions 28, in the longitudinal direction 6 bythe front face 36 of the second element 22, said second element 22covering the grooves 30 to form the feeding channels 42, and in thelongitudinal direction 4 by the bottom of the second section 26 carryingthe protrusions 28.

In FIG. 2, the feeding channels 42 comprise a first section 48 abuttingthe fluid chamber 40 and a second section 50 following the first section48 in the flow direction and radial direction 10, respectively. Thesecond section 50 abuts the swirl chamber 44 with the exit end 46. Asshown in FIG. 2, the width w1 of the first section 48 decreases in theflow direction and the radial direction 10. In contrast to this, thewidth w2 of the second section 50 is constant or decreases to a lesserextent than the first section 48 in the flow direction and radialdirection 10.

The protrusions 28, which form the side walls of the first sections 48,include an angle α, between the protrusions' side walls as shown. InFIG. 2, there is further indicated a centerline 52 of the second section50 extending in the radial directions 8, 10. Said centerline 52subdivides the angle α into a first angle α1 and a second angle α2. Themaximum difference between the first angle α1 and the second angle α2 is10°, more preferably 5° or 1°, most preferably 00. Due to the bulged outfront face 36 of the second element 22, the height h of the firstsection 48 or/and second section 50 of the feeding channels 42 decreasesin the flow direction and the radial direction 10. Further, the length 1of the second section 50 in the flow direction and the radial direction10 is equal to or smaller than the width w2 of the second section 50. Inaddition, the width w2 of the second section 50 is equal to the height hof the second section 50.

As shown in FIG. 3, in the transition region between the supportsurfaces 32 and the side surfaces 34 the protrusions 28 comprise aradius r1. In order to have a compact cross-sectional form, the ratio ofthe radius r1 to the width w, e. g. w1 or w2, of the feeding channel 42is equal to or less than ⅓, more preferably equal to or less than ¼,most preferably equal to or less than ⅕.

Even if the first element 20 and the second element 22 are assembled,they are still movable relative to each other into different relativepositions. In the shown embodiment, the elements 20 and 22 may be movedin the longitudinal direction 4, 6 relative to each other. By thisrelative movement the form, dimensions or/and justification of thefeeding channels 42 or/and the swirl chamber 44 is changed byelastically deforming the protrusions 28 or/and the bottom of secondsection 26 of the first element 20, i.e. by elastically deforming theelastic portion of the first element 20. In other words, it is easy tochange the behavior of the spray nozzle 2. Further, there are providedmeans (not shown) for locking the elements 20, 22 in their differentrelative positions.

With reference to FIG. 4, the afore-mentioned outlet channel 18 in thesecond section 26 of the first element 20 comprises an entrance end 54facing the swirl chamber 44 in the longitudinal direction 6 and an exitend 56 for discharging the fluid to the environment 58 of the spraynozzle 2 and the sprayer, respectively, in the longitudinal direction 4.The outlet channel 18 tapers steadily in the flow direction and thelongitudinal direction 4. Thus, the outlet channel 18 comprises at leastone tapering portion, i.e. the outlet channel 18 is tapered in at leastpart along the length of the outlet channel 18 toward the exit. Thetapering may be continuous or in steps, and may be angled or curved. Inthe shown embodiment, the tapering portion abuts the exit end 56 as wellas the entrance end 54 of the outlet channel 18, so that the wholeoutlet channel tapers in the flow direction. The edge 60 surrounding theexit end 56 has a radius r₂. The radius r₂ is smaller than 0.03 mm,preferably smaller than 0.02 mm.

Further, the exit end 56 has a maximum diameter between 0.12 mm and 0.15mm and more preferably a diameter about 0.14 mm with a correspondingmaximum cross-sectional area to achieve an average particle size byvolume (D₅₀) with a flow rate higher than 0.24 g/s at 9 bar (for thefluid water is considered), which is equal or lower than 60 am, orpreferably equal or lower than 50 am, or more preferably equal or lowerthan 45 μm. This diameter further achieves an average particle size byvolume (D₃₂) which is equal or lower than 50 am, or preferably equal orlower than 45 am, or more preferably equal or lower than 40 am. Theaverage percentage of particles having a diameter smaller than 10 μm(%<10 μm) is less than 2%, preferably less than 1.5%, more preferablyless than 1%.

A bigger geometry of the nozzle having a diameter (d_(max)) about 0.8 mmand, thus, providing a higher flow rate, e.g. higher than 3.2 g/s at 2bar, achieves an average particle size by volume (D₅₀) (for the fluidwater is considered) which is equal or lower than 120 lam, or preferablyequal or lower than 115 μm. This diameter further achieves an averageparticle size by volume (D₃₂) which is equal or lower than 100 am, orpreferably equal or lower than 96 am. The average percentage ofparticles having a diameter smaller than 10 μm (%<10 μm) is less than1.5%, preferably less than 1%, more preferably less than 0.5%.

Above this, the outlet channel 18 has an inner face 62 surrounding theoutlet channel 18 and limiting the same in the radial direction 8. Theinner face 62 of the outlet channel 18 includes an angle β, said angle βpreferably varying between 70° and 130°, preferably between 80° and120°, more preferably between 80° and 110°.

As shown in FIG. 4, the degree of tapering of the outlet channel 18 isconstant in the flow direction and the longitudinal direction 4. In theshown embodiment this is achieved by at least a tapering portion of theoutlet channel 18 or the whole outlet channel 18 having the form of atruncated cone or a truncated pyramid. It has further been found out,that the pressure drop, i.e. energy dissipation in the spray nozzle 2could be reduced and a further reduction of the minimum pump pressurefor dispensing the fluid could be achieved by adjusting the ratio of thesum of the cross-sectional areas of the feeding channels 42 at theirexit end 46 to the cross-sectional area of the exit end 56 of the outletchannel 18. This ratio is between about 1.5 and about 2.7, preferablybetween about 1.7 and about 2.6. Further, the ratio of the diameterd_(s) of the swirl chamber 44 to the diameter d_(max) of the exit end 56of the outlet channel 18 is about 2.5 to about 3.5.

FIG. 5 shows the enlarged section A of FIG. 1 with a first modification.In the following only the differences will be described, the samereference signs will be used for similar or the same components and theabove description of the first embodiment applies accordingly in thisregard.

In contrast to the outlet channel 18 described with reference to FIG. 1to 4, the degree of tapering of outlet channel 18 according to FIG. 5decreases in the flow direction and the longitudinal direction 4. Thisis achieved by providing an inner face 62 of the outlet channel 18 beingcurved in the flow direction and the longitudinal direction 4. In theembodiment according to FIG. 5, at least a tapering portion of theoutlet channel 18 or the whole outlet channel 18 has the form of atruncated hyperboloid of revolution.

FIG. 6 shows a second embodiment of the spray nozzle according to theinvention. Since the second embodiment at least partially corresponds tothe first embodiment according to FIG. 1 to 5, in the following only thedifferences will be described, the same reference signs will be used forsimilar or the same components and the above description of the firstembodiment applies accordingly in this regard.

The spray nozzle 2 according to FIG. 6 comprises at least three layers,i.e. an outlet layer 64 with a first hole 66, a channel layer 68 with asecond hole 70 and slots 72 and an inlet layer 74 with slot-like holes76, said layers 64, 68 and 74 being sandwiched, while the inlet layer 74is shown in a transparent manner in FIG. 6 to increase theintelligibility of the drawing. Being sandwiched this way, the firsthole 66 forms the outlet channel 18, the second hole 70 forms the swirlchamber 44, the slots 72 form the feeding channels 42 and the holes 76in the inlet layer form inlet holes for feeding the fluid from the fluidchamber 40 into the feeding channels 42. In the shown embodiment, thelayers 64, 68 and 74 are separable from each other and each of thelayers 64, 68 and 74 could be replaced, so that the layers 64, 68 and 74could also be regarded as separate discs with corresponding slots andholes.

As shown in FIG. 6, there is provided an overlapping area 78 between theinlet holes 76 and the feeding channels 42 when viewed in thelongitudinal direction 4. The inlet layer 74 and the channel layer 68are moveable—in this case rotatable around the longitudinal axis16—relative to each other, while the inlet holes 76 and the feedingchannels 42 are formed such that, the distance between the overlappingarea 78 and the swirl chamber 44 could be reduced by rotating the inletlayer 74 relative to the channel layer 68 in the circumferentialdirection 14 and could be enlarged by rotating the inlet layer 74relative to the channel layer 68 in the circumferential direction 12.Thus, the distance between the overlapping area 78 and the swirl chamber44 is adjustable.

FIG. 7 shows a third embodiment of the spray nozzle 2 according to theinvention. Since the third embodiment at least partially corresponds tothe second embodiment according to FIG. 6, in the following only thedifferences will be described, the same reference signs will be used forsimilar or the same components and the above description of the firstand second embodiment applies accordingly in this regard.

In contrast to the second embodiment, the inlet holes 76 and the feedingchannels 42 of the third embodiment are formed such that, the size ofthe overlapping area 78 could be reduced by rotating the inlet layer 74relative to the channel layer 68 in the circumferential direction 12 andcould be enlarged by rotating the inlet layer 74 relative to the channellayer 68 in the circumferential direction 14. Thus, the size of theoverlapping area 78 is adjustable.

It should be mentioned that the principles of the second and thirdembodiment could also be advantageously combined in a single spraynozzle 2, so that the size of the overlapping area 78 as well as thedistance between the overlapping area 78 and the swirl chamber 44 couldbe adjusted by a relative movement between the inlet layer 74 and thechannel layer 68.

The spray nozzle 2 is made of a plastic material, e.g. polyoxymethylene,polypropylene, polyethylene, polystyrene, acrylonitrile butadienestyrene, silicone, polyamide, polyethylene terephthalate or mixturesthereof. Further, the spray nozzle can additionally comprise anelastomer.

According to the invention, the spray nozzle 2 should be used in asprayer, said sprayer preferably being a hand operated sprayer, forexample a trigger sprayer, the sprayer more preferably comprising afluid container being manually squeezable, a sprayer with a pressurizedfluid storage container or a manually actuable pumping device, or in anelectrically driven sprayer.

Pin bending and compression are problems that occur during themanufacturing process of spray nozzles having an exit end with adiameter (d_(max)) smaller than 0.25 mm, in particular smaller than 0.2mm and even smaller than 0.15 mm. Therefore, high precision is requiredduring the assembly of the pin 22 and nozzle cup 20. Thus, the spraynozzle 2 is produced by a precise injection molding process. In order toform the nozzle cup 20, the pin 22 (molding tool) is centered in acounter tool by an autopositioning process. The tapering, i.e. conicalshape of the pin 22 facilitates centering of the molding tool in thecounter tool as compared to a nozzle having a cylindrical pin. Inaddition, a conical molding tool (pin) is more robust than a cylindricalone. Further, in order to provide an edge surrounding the exit end 56with a radius being smaller than 0.03 mm, preferably smaller than 0.02mm, micro erosion is applied for the tool manufacturing.

Method of Making a Hairspray

First two solutions are made: a main mix and a second mix. The main mixcomprises the hairstyling polymer(s), which are dissolved with stirringin water and components of the preservative system. A second mix iscreated which comprises water and the paraben-based preservativecomponent(s) (e.g. methyl paraben). Optionally the second mix is heatedup in a microwave to 90 to 95° C. in order to dissolve the paraben. Thetwo mixes are then combined to create the hairstyling formulation. Thehairstyling formulation is then put into the container and thencontainer is sealed by crimping on a sealing mounting cup which includesa valve system. Then the propellant is added under pressure and then thespray nozzle is added to the container.

Examples

Examples 1 2 3 4 5 6 7 8 Acrylates/hydroxyesters 6.7 5.5 3.6 — 3.35 — —0.2 acrylates copolymer ¹ Polyurethane- 14/AMP- — — 3.0 10.0 6.0 10.0 —6.0 acrylates polymer blend ² Acrylates Copolymer ³ — — — 5.6 — 1.7 4.11.0 2-Aminopropanol (AMP) 0.6 0.25 0.17 0.35 0.15 0.2 0.3 0.25 Castoroil PEG-40 H, (90%) 0.1 0.2 0.15 0.3 0.3 0.3 0.2 0.15 Disodium EDTA 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Perfume 0.2 0.07 0.3 0.15 0.10.05 0.1 0.15 Phenoxyethanol ⁴ 0.3 0.2 0.3 0.3 0.4 0.2 0.2 0.21,3-bis(hydroxymethyl)-5,5- — 0.1 0.2 0.4 0.2 0.3 0.4 0.3dimethylimidazolidine-2,4- dione ⁵ Methylparaben ⁶ 0.2 — — — 0.2 0.2 0.20.2 Deionised water Add to 100 Add to 100 Add to 100 Add to 100 Add to100 Add to 100 Add to 100 Add to 100 Examples 9 10 11 12 13 14 15 16Acrylates/hydroxyesters 4.69 4.8 4.0 — — 2.0 3.6 — acrylates copolymer ¹Polyurethane- 14/AMP- — — 7.0 — 7.0 6.0 7.0 — acrylates polymer blend ²Acrylates Copolymer ³ — — — 5.1 3.9 — — 6.5 2-Aminopropanol (AMP) 0.42 0.49 0.4 0.38  0.25 0.21 0.37 0.53 Castor oil PEG-40 H, 0.1  0.2 0.30.3 0.1 0.3 0.2 0.3 (90%) Disodium EDTA 0.07 — — —  0.07 0.1 0.1 0.1Perfume 0.07 0.1  0.07 0.15  0.05 0.035 0.03 0.08 Phenoxyethanol ⁴ 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 1,3-bis(hydroxymethyl)- —  0.29  0.29 0.29 —0.29 0.29 0.29 5,5-dimethylimidazolidine- 2,4-dione ⁵ Methylparaben ⁶0.1  — — — 0.1 0.14 0.14 0.2 Ethanol — — — 1 — — — — DME 30    30   30  28 30   30 30 40 Deionised water Add to 100 Add to 100 Add to 100 Add to100 Add to 100 Add to 100 Add to 100 Add to 100 Key: ¹ = Acudyne ® 1000(45% solution); ² = DynamX H₂O ® (25% solution); ³ = Balance ® CR (45%solution); ⁴ = Euxyl ® PE 9010; ⁵ = Nipaguard ® DMDMH; ⁶ =PHB-methylester from Schütz.

Any of examples 1 to 8 may be placed in a predominantly plastic orpredominantly metal container. The propellant may be a compressed gaspropellant such that the product comprises 15% or less VOC by totalweight of the hairstyling formulation and propellant. The sprayingdevice may comprise the spray nozzle of claim 8.

Any of examples 9 to 16 may be placed in container wherein the containerwall comprises at least about 80% metal material by total weight of thecontainer. The metal material may be selected from the group consistingof: aluminium, tin plated steel, and combinations thereof. Thepropellant is DME as stated in the table.

Performance Data

Experiment 1—Sensory Data

Aerosol hairspray products pursuant to the present invention comprisinghairstyling formulations selected from the above example section werecompared with a standard aerosol hairstyling product with excellentperformance. The standard aerosol hairspray product comprises: 50% DMEpropellant, the container is a metal container, a hairspray formulationcomprising 3% Amphomer as hairstyling polymer, circa 38% ethanol, andless than 1% water; and wherein the product comprises VOC 95% (thesepercentages are by total weight of the hairstyling formulation andpropellant).

The ejected compositions from these products are sprayed onto hair andcompared for sensory criteria. When the difference between the productpursuant to the present invention and the standard product is from −1 to+1 (i.e. one point better or worse), then an equals sign (=) is marked.When the difference is less than −1 or greater than +1 then a − or a +is marked, respectively. When the difference is greater than +2, then a++ is marked.

Hairstyling Hairstyling Hairstyling formulation formulation formulationCriteria of Ex. 4 of Ex. 9 of Ex. 13 Spraying device Comprises ComprisesComprises the spray a vapour a vapour nozzle of housing hole. housinghole. claim 8. Approx. VOC (%) <1 30 30 Propellant Nitrogen DME DMETotal hairstyling  5  3  5 polymer amount (%) INITIAL HOLD ¹ = = =DRYING TIME ² = = = FEEL ³ ++ ++ ++ LOOK ⁴ = = = LOOK ⁵ = = = FEEL ⁶ = == FEEL ⁷ = = = Key: ¹ = Hold on mannequin (least hold to most hold); ² =Humidity after application (hair feels very dry to hair feels very wet);³ = Stickiness of hands/hair (not sticky at all to very sticky); ⁴ =Hair look mannequin (very natural to very clumped); ⁵ = Residues onmannequin hair (no residues at all to lots of residues); ⁶ = Hair feelof mannequin after combing (very rough to very smooth); ⁷ = Drawingfingers through hair of mannequin (hair clumped together to hair freeflowing).Experiment 2—Technical Data

The setting and the hold conferred to a hairstyle by a composition canbe determined by measuring, respectively, the 3-point bending force andthe hold force factor. 3-point bending force methodology: 0.5 ml/ghairstyling formulation is applied to the hair tress and massaged in for1 min. The hair tresses are then dried in a drying cabinet for 45 min at45° C. The tresses are then smoothed over by the fingers and driedovernight in a chamber at 20° C. at 65% relative humidity. Themeasurement is made with stamp at 5 positions on the sample. The 3-pointbending force is measured according to the methodology detailed in F.Frosch, F. Vogel, 6^(th) International Hair Science Symposium Of theGerman Wool Research Institute, Luneburg/Germany (1988). See also themethodology DIN-EN-658-5 from the American National Standards Institute.A mean value is calculated after 9 repeats are performed (i.e. n=9).

Hold force factor (also known as curl retention) methodology: 0.5 ml/ghairstyling formulation is applied to the hair tress and massaged in for1 min. Each hair tress is then adjusted to 50% by weight of the hairtress and combed three times. The tresses are plaited and dried in adrying cabinet for 45 min at 45° C. The tresses are then dried overnightin a climatic chamber at 20° C. at 65% relative humidity. The curlretention measurements are taken the following day. The climaticconditions are: 20° C. at 85% relative humidity. The reading times are:after 0 h, 1 h, 2 h, 3 h 5 h and 24 h (h means hour). The hold forcefactor is measured according to the methodology detailed in C.R.Robbins, Chemical and Physical Behavior of Human Hair, 3^(rd) edition,page 352, Springer-Verlag, New York (1994). A mean value is calculatedafter 3 repeats are performed (i.e. n=3).

Table X details the 3-point bending force and the hold factor after 1 h,5 h and 24 h of the hairstyle, after applying the below-detailedhairstyling formulations. Where indicated, the hairstyling formulationis as per an example from the table in the examples section above.Samples A to D were treated with hairstyling formulations A to D, whichcomprise the indicated hairstyling polymer in deionised water. Totalhairstyling polymer present is indicated in brackets. Samples α to γ(alpha to gamma) were control treatments as detailed below.

TABLE X Sample Hairstyling polymer [wt % of total hairstyling polymer] DEx. 4 Mixture of ¹ Mixture of ³ alpha beta gamma A ⁵ B ² C ³ and ² (1:1Ex. 1 ¹ and ² (1.1 (α) (β) ⁵ (γ) ⁶ Parameters [3%] [3%] [3%] ratio) [3%][3%] ratio) [5%] N/T [3%] [3%] 3-point bending force (N) 2.101 +/− 2.48+/− 3.02 +/− 2.216 +/− 2.231 +/− 3.211 +/− 0.09 +/− 1.82 +/− 1.95 +/− 1break - hold 0.413 0.60 0.70 0.449 0.358 0.796 0.01 0.62 0.628 3-pointbending force (%) 50.70 +/− 55.53 +/− 41.55 +/− 43.33 +/− 57.61 +/−41.34 +/− 92.76 +/− 49.97 +/− 51.81 +/− 3rd break - elasticity 7.46 8.133.53 4.13 5.32 6.87 19.32 11.00 12.56 Hold factor (%) after 0 h 88.17+/− 91.81 4 +/− 90.72 +/− 94.00 +/− 95.02 +/− 91.34 +/− 77.37 +/− 89.66+/− 90.65 +/− 0.13 1.791 5.59 1.79 1.46 4.58 1.94 4.12 1.83 Hold factor(%) after 1 h 70.95 +/− 82.73 +/− 74.6 +/− 83.39 +/− 85.25 +/− 82.95 +/−30.98 +/− 55.46 +/− 52.21 +/− 4.64 2.026 4.88 0.90 2.44 6.92 1.87 2.598.99 Hold factor (%) after 5 h 54.18 +/− 70.77 +/− 57.61 +/− 71.94 +/−76.35 +/− 67.89 +/− 10.12 +/− 16.58 +/− 14.72 +/− 7.83 6.45 4.89 1.822.75 3.92 0.51 1.97 1.52 Hold factor (%) after 24 h 50.75 +/− 60.9 +/−51.04 +/− 67.31 +/− 73.58 +/− 65.19 +/− 7.50 +/− 12.53 +/− 11.51 +/−7.71 3.899 4.7 1.16 2.64 7.10 1.08 2.94 1.08 Key: ¹ = Acudyne ® 1000; ²= DynamX ® H2O; ³ = Balance ® CR; ⁴ = Amphomer ®; N/T = not treated; ⁵ =PVP/VA (vinylpyrrolidone/vinylacetate copolymer) 64; ⁶ = PVP(polyvinylpyrrolidone) K30.

Conclusions from experiment 2 include: the samples left untreatedexhibited the weakest (i.e. lowest) 3-point bending force and holdfactor. PVP VA 64 and PVP K30 are softer hairstyling polymers, which, inthe context of the hairstyling formulation pursuant to the presentinvention provide weaker hold as well as lower humidity resistance. Thehard hairstyling polymers, especially the blends, show high humidityresistance—see hold factor values after 24 h in table X.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. An aerosol hairspray product for styling and/orshaping hair wherein the product comprises: i. a container comprising acontainer wall which encloses a reservoir for storing a hairstylingformulation and a propellant; ii. the hairstyling formulationcomprising: (a) from ab out 50% to about 99% water by total weight ofthe hairstyling formulation and propellant; (b) from about 1% to about16% of two neutralized hairstyling polymers by total weight of thehairstyling formulation and propellant, wherein the neutralizedhairstyling polymers are selected from acrylates copolymer,acrylates/hydroxyesters acrylates copolymer,polyurethane-14/AMP-acrylates polymer blend, (c) a liquefied gaspropellant; wherein the hair styling formulation is free of ethanolwherein the hairstyling formulation comprises less than 0.5% of acationic surfactant by total weight of the hairstyling formulation andpropellant; iii. a spraying device attached to the container fordispensing the hairstyling formulation from the reservoir of thecontainer.
 2. The aerosol hairspray product of claim 1, wherein thehairstyling formulation comprises from about 25% to about 45%propellant, by total weight of the hairstyling formulation andpropellant and wherein the propellant comprises dimethylether.
 3. Theaerosol hairspray product of claim 1, wherein the hairstylingformulation comprises a kinematic viscosity from about 1 mm²/s to about15 mm²/s, measured according to standard test DIN EN ISO
 3104. 4. Theaerosol hairspray product of claim 3, wherein the hairstylingformulation comprises a kinematic viscosity from about 1 mm²/s to about10 mm²/s, measured according to standard test DIN EN ISO
 3104. 5. Theaerosol hairspray product of claim 4, wherein the hairstylingformulation comprises a kinematic viscosity from about 1 mm²/s to about4 mm²/s, measured according to standard test DIN EN ISO
 3104. 6. Theaerosol hairspray product according to claim 1, comprising from about 3%to about 8% of the neutralized hairstyling polymer, by total weight ofthe hairstyling formulation and propellant.
 7. The aerosol hairsprayproduct according to claim 1, wherein the pressure inside the containeris from about 8 bar to about 10 bar, at 50° C.
 8. A method for stylinghair comprising: i. applying to hair an ejected composition, wherein theejected composition is ejected by the aerosol hairspray productaccording to claim 1; ii. drying the ejected composition on the hair.